U.S. patent application number 13/879264 was filed with the patent office on 2013-10-17 for anti-allergen agent.
This patent application is currently assigned to TOAGOSEI CO., LTD.. The applicant listed for this patent is Yoshinao Yamada. Invention is credited to Yoshinao Yamada.
Application Number | 20130273798 13/879264 |
Document ID | / |
Family ID | 45938380 |
Filed Date | 2013-10-17 |
United States Patent
Application |
20130273798 |
Kind Code |
A1 |
Yamada; Yoshinao |
October 17, 2013 |
ANTI-ALLERGEN AGENT
Abstract
Conventional tannic acid and polyphenol anti-allergen agents are
known as anti-allergen agents capable of deactivating allergens
such as mites and pollen, but these agents have inferior heat
resistance and pose problems with coloration, discoloration and
elution. The purpose of the present invention is to provide an
anti-allergen agent that has excellent heat resistance, shows no
coloration, and has excellent water resistance and workability. It
was discovered that using an inorganic substance having a high acid
site concentration with acid site concentration being defined as
the number of acid sites having a pKa of 4.8 or less, it is
possible to realize an anti-allergen that manifests strong
anti-allergen effects, has excellent heat resistance and water
resistance, shows little coloration, and has excellent
workability.
Inventors: |
Yamada; Yoshinao;
(Nagoya-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Yamada; Yoshinao |
Nagoya-shi |
|
JP |
|
|
Assignee: |
TOAGOSEI CO., LTD.
Tokyo
JP
|
Family ID: |
45938380 |
Appl. No.: |
13/879264 |
Filed: |
October 13, 2011 |
PCT Filed: |
October 13, 2011 |
PCT NO: |
PCT/JP2011/073508 |
371 Date: |
July 3, 2013 |
Current U.S.
Class: |
442/123 ;
252/88.2 |
Current CPC
Class: |
C09D 5/1618 20130101;
C09D 7/67 20180101; C09D 7/62 20180101; C09D 7/69 20180101; D06M
11/71 20130101; D06M 11/46 20130101; Y10T 442/2525 20150401; D06M
11/79 20130101; C09D 5/14 20130101 |
Class at
Publication: |
442/123 ;
252/88.2 |
International
Class: |
D06M 11/79 20060101
D06M011/79; D06M 11/46 20060101 D06M011/46; D06M 11/71 20060101
D06M011/71 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 14, 2010 |
JP |
2010-231123 |
Claims
1.-8. (canceled)
9. An anti-allergen agent comprising an inorganic powder having a
concentration of acid sites with a pKa of no greater than 4.8 of at
least 0.001 mmol/g but no greater than 10 mmol/g.
10. The anti-allergen agent according to claim 9, wherein the
inorganic powder has a median diameter, measured by a laser
particle size distribution analyzer and calculated on a volumetric
basis, of at least 0.01 .mu.m but no greater than 50 .mu.m.
11. The anti-allergen agent according to claim 9, wherein the
inorganic powder has a pH as a 5 wt % aqueous dispersion of at
least 3 but no greater than 9.
12. The anti-allergen agent according to claim 9, wherein the
inorganic powder is at least one selected from an amorphous
magnesium silicate, an .alpha.-type zirconium phosphate, and an
activated titanium oxide.
13. The anti-allergen agent according to claim 9, wherein the
inorganic powder is an amorphous magnesium silicate.
14. The anti-allergen agent according to claim 9, wherein the
inorganic powder has a concentration of acid sites with a pKa of no
greater than 4.8 of at least 0.01 mmol/g but no greater than 10
mmol/g.
15. The anti-allergen agent according to claim 9, wherein the water
content of the inorganic powder is at least 0.5 wt %.
16. A method for inactivating an allergen comprising: a step of
preparing an anti-allergen agent, and a step of directly contacting
the anti-allergen agent with an allergen, wherein the anti-allergen
agent comprising an inorganic powder having a concentration of acid
sites with a pKa of no greater than 4.8 of at least 0.001 mmol/g
but no greater than 10 mmol/g.
17. The method for inactivating an allergen according to claim 16,
wherein the inorganic powder has a median diameter, measured by a
laser particle size distribution analyzer and calculated on a
volumetric basis, of at least 0.01 .mu.m but no greater than 50
.mu.m.
18. The method for inactivating an allergen according to claim 16,
wherein the inorganic powder has a pH as a 5 wt % aqueous
dispersion of at least 3 but no greater than 9.
19. The method for inactivating an allergen according to claim 16,
wherein the inorganic powder is at least one selected from an
amorphous magnesium silicate, an .alpha.-type zirconium phosphate,
and an activated titanium oxide.
20. The method for inactivating an allergen according to claim 16,
wherein the inorganic powder is an amorphous magnesium
silicate.
21. The method for inactivating an allergen according to claim 16,
wherein the inorganic powder has a concentration of acid sites with
a pKa of no greater than 4.8 of at least 0.01 mmol/g but no greater
than 10 mmol/g.
22. The method for inactivating an allergen according to claim 16,
wherein the water content of the inorganic powder is at least 0.5
wt %.
23. A coating composition comprising the anti-allergen agent
according to claim 9 and a binder or a paint.
24. The coating composition according to claim 23, wherein it has a
pH of at least 3 but no greater than 9.
25. An anti-allergen product processed using the coating
composition according to claim 23.
26. An anti-allergen fabric processed using the coating composition
according to claim 23.
Description
TECHNICAL FIELD
[0001] The present invention relates to an anti-allergen agent
comprising an inorganic powder having a specific concentration of
acid sites and to an anti-allergen composition and a product
comprising the anti-allergen agent. The anti-allergen agent can
impart an effect in reducing allergy-causing substances due to
mites, pollen, etc. to fiber products such as clothing, bedding,
and masks, filters used in air cleaners, air conditioners, etc.,
interior products such as curtains, carpets, and furniture,
automotive interior materials, etc. by means of spraying or
coating, or by fixing to a surface layer of building materials such
as wallpaper and flooring materials.
BACKGROUND ART
[0002] In recent years, the number of people suffering from
allergic diseases such as pollen allergy due to Cryptomeria
japonica pollen, etc., bronchial asthma due to house dust caused by
mites, etc., hay fever, allergic rhinitis, and atopic dermatitis
has been increasing and is becoming a serious problem. As methods
for treating such allergic diseases, there has been great progress
as a result of the development of the series of medicinal agents
called anti-allergic drugs, and steroids for inhalation or external
use, but these are still only symptomatic treatments and not
curative treatments.
[0003] Furthermore, a miticide, etc. is generally used for the
eradication of house dust mites, but Dermatophagoides farinae,
Dermatophagoides pteronyssinus, etc. in house dust have the
characteristics that not only the mites' bodies but also the feces
and remains thereof cause an allergy reaction, and since fine
allergen particles are gradually released as the remains decompose
after death, merely killing mites cannot inactivate the allergens.
Moreover, masks are used for preventing inhalation of the pollen of
Cryptomeria japonica, etc., but since the allergen activity of
pollen attached to the mask does not disappear, there is a risk of
inhalation when the pollen is scattered again.
[0004] Because of such problems, in order to alleviate the symptoms
of an allergic disease or prevent new sensitization, it is
necessary to remove allergens, which are the substances causing
allergic symptoms, from a living space before they are inhaled into
the human body, or render them harmless by modification.
[0005] As a method for removing an allergen without using a
medicinal agent, there is a method in which the amount of allergen
is lessened by physically removing floor-deposited dust or
air-suspended dust by suction with a vacuum cleaner or an air
purifier. However, a large amount of allergen sucked up by a vacuum
cleaner is simply stored in a dust bag, and it can be expected that
there will be a risk of rescattering the allergen when disposing of
the dust bag. Furthermore, it is difficult to completely remove a
fine particulate substance by removal using an air purifier, and
there is a risk of it being rescattered.
[0006] Consequently, an anti-allergen agent that inactivates a
harmful allergen to make it harmless by the action of adsorption on
or covering of a reactive site of the allergen with an antibody has
recently been proposed. For example, methods employing tannic acid
are disclosed in Patent Documents 1 and 2, Non-Patent Document 1,
etc., and Patent Document 3 discloses a polyphenol such as gallic
acid and tea extract, which is an analogous compound to tannic
acid. However, an organic allergen-reducing agent such as tannic
acid is chemically unstable, and there are the problems that when
it is attached to fiber or fiber products, coloration might occur
or it might change in color over time, or it might bleed out to the
environment due to water, oil, solvent, or washing, thus causing
coloration of clothing or skin irritation. For example, Patent
Document 1 discloses that tannic acid can be removed by distilled
water, and it is thus clear that when a fiber treated with tannic
acid is washed repeatedly the tannic acid is lost. Therefore, there
is a problem with the use thereof as an anti-allergen agent in
fiber or fiber products that have a possibility of being washed or
being in direct contact with the skin, and there is the drawback
that application targets are limited for fiber products that are
exposed to view because of problems with color tone, heat
resistance, or durability. As one that improve the above defects,
an anti-allergen agent comprising an inorganic substance has been
proposed. Patent Document 4 discloses that allergen can be adsorbed
using an inorganic substance such as activated charcoal, but a
substance, such as activated charcoal, that exhibits adsorption
based on the principle of physical adsorption due to it having a
large porous specific surface area usually shows low anti-allergen
adsorption performance and is black, and its application is
therefore limited, which is a problem. Furthermore, Patent Document
5 discloses that, among inorganic substances, one having a high
solid acid strength has excellent anti-allergen activity. However,
even with substances showing the same level of solid acid strength,
the allergen inactivation performance can vary to a great extent in
practice, and one having higher solid acid strength does not always
exhibit better anti-allergen activity. Furthermore, it has become
clear that when a fiber is processed in an aqueous system using a
solid acid having very high solid acid strength, metal sections of
processing equipment might be corroded, which is a problem.
PRIOR ART DOCUMENTS
Patent Documents
[0007] Patent Document 1: JP-A-61-44821 (JP-A denotes a Japanese
unexamined patent application publication) [0008] Patent Document
2: JP-B-2-16731 (JP-B denotes a Japanese examined patent
application publication) [0009] Patent Document 3: JP-A-6-279273
[0010] Patent Document 4: JP-A-2002-167332 [0011] Patent Document
5: WO2009/044648
Non-Patent Documents
[0011] [0012] Non-Patent Document 1: `Sosetsu Tanninnikansuru
Saikinnokenkyu` (Review of Recent Research into Tannin), Yakugaku
Zasshi, 103 (2), 125-142 (1983)
SUMMARY OF INVENTION
[0013] In light of the above circumstances, the object of the
present invention is to provide an anti-allergen agent comprising
an inorganic substance that has high anti-allergen performance and
excellent heat resistance and ease of processing, causes hardly any
coloration, and is not leached out by water, and is preferably an
anti-allergen agent that causes hardly any change in color or
corrosion of equipment when used as a coating composition or a
resin composition, and to provide an anti-allergen composition and
an anti-allergen product using same.
[0014] As a result of an intensive investigation by the present
inventors in order to solve these problems, it has been found that
an inorganic powder having a concentration of acid sites with a pKa
of no greater than 4.8 of at least 0.001 mmol/g exhibits high
anti-allergen activity, and the present invention has thus been
accomplished. The present invention is an anti-allergen agent
comprising an inorganic powder having a concentration of acid sites
with a pKa of no greater than 4.8 of at least 0.001 mmol/g, and an
anti-allergen composition and an anti-allergen product using the
anti-allergen agent.
DESCRIPTION OF EMBODIMENTS
[0015] The present invention is explained below.
[0016] The concentration of acid sites referred to with respect to
the anti-allergen agent of the present invention is the number of
acid sites or acidic centers on a solid surface and is usually
expressed as a number of moles or a number per unit weight or unit
surface area of a solid. The acid strength of an acid site used for
calculation of the concentration of acid sites can be expressed as
pKa. The acid strength represents the strength of the property of
an acid site on a solid surface of donating a proton to a base or
the property of accepting an electron pair from a base; the smaller
the pKa of an acid site, the stronger the property of donating a
proton to a base or the property of accepting an electron pair from
a base, and the higher the ability to inactivate an allergen
protein by adsorbing it.
[0017] However, usually, while one acid site is adsorbing one
allergen protein it cannot adsorb another allergen protein; even
when each acid site has a high acid strength, if the number of acid
sites, that is, the concentration of the acid sites, is low,
adsorption soon reaches saturation and a sufficient anti-allergen
effect cannot be exhibited. When there is a large amount of
allergen protein, if the quantity thereof adsorbed, that is, the
concentration of acid sites, is high, a high anti-allergen effect
is exhibited.
[0018] On the other hand, when the acid strength of an acid site is
small, that is, when the pKa is large, the strength of the property
of donating a proton to a base or the property of accepting an
electron pair from a base is weakened; when the pKa is too large,
the ability of each acid site in adsorbing an allergen protein and
inactivating it becomes low, and even if the number of acid sites,
that is, the concentration of the acid sites, is large, it becomes
difficult for allergen protein to be fully adsorbed. Although this
balance also depends on the structure of the allergen protein and
the compatibility between a base and an acid site, as a result of
examining representative allergen proteins in the present
invention, when an inorganic substance having an acid site has a
pKa for the acid site of no greater than 4.8, it exhibits an
inactivating effect toward any allergen protein, and the number of
acid sites, that is, the concentration of acid sites, correlates
with the anti-allergen effect irrespective of the type of allergen
protein. That is, it has been found that a measurement of the
concentration of acid sites of a solid acid having a pKa for the
acid sites of no greater than 4.8 can be used as an indicator for
the anti-allergen performance of the substance.
[0019] More specifically, with regard to the anti-allergen agent of
the present invention, the number of acid sites of an inorganic
substance powder having a pKa for the acid sites of no greater than
4.8 is defined as the `concentration of acid sites` in the present
invention; the larger this value, the higher the anti-allergen
performance, and the more preferable it is as an anti-allergen
agent. Specifically, one having a concentration of acid sites of at
least 0.001 mmol/g is preferable. There is no upper limit for the
concentration of acid sites that should not be exceeded, but since
no inorganic substance powder that exceeds 10 mmol/g is usually
known as a specific material, the upper limit is usually no greater
than 10 mmol/g.
[0020] With regard to measurement of the number of acid sites
having a pKa of no greater than 4.8, by applying a titration method
using an indicator that corresponds to a pKa of 4.8, the total of
all acid sites having a pKa of no greater than 4.8 can be measured,
and this value is defined as the concentration of acid sites having
a pKa of no greater than 4.8. In the present invention, the
concentration of acid sites is preferably at least 0.01 mmol/g, and
more preferably at least 0.05 mmol/g. In particular, an inorganic
substance having a concentration of acid sites of at least 0.05
mmol/g has an excellent anti-allergen effect and exhibits a high
effect for various allergen substances.
[0021] The concentration of acid sites of a powder may be
determined by measuring the amount of base that reacts with the
powder. There are methods in which measurement is carried out in a
liquid phase or a gas phase; a titration method is known as a
method for measurement in a liquid phase, and there is known as a
method for measurement in a gas phase a gas chemical adsorption
method such as a method in which the difference between the amount
of He or hydrogen gas adsorbed and desorbed and the amount of a
basic gas adsorbed and desorbed is measured. The reaction between
an anti-allergen agent and an allergen in the present invention is
a reaction employing a liquid as a medium, and measurement by a
titration method in a liquid phase is therefore suitable.
[0022] A method for measuring the concentration of acid sites of an
inorganic powder by a titration method in a liquid phase is as
follows.
[0023] An inorganic powder dispersed in a nonpolar solvent is
titrated using n-butylamine, and the end point of the titration is
confirmed by a change in color of an indicator. The indicator prior
to reaction exhibits a color due to its base form, but when it is
adsorbed on an inorganic powder it exhibits a color due to it being
in a conjugate acid form. The amount of n-butylamine titrated that
is required to change the color due to the conjugated acid form to
the color due to the base form is used to determine the
concentration of acid sites. One acid site of a solid corresponds
to one n-butylamine molecule. Since the base for titration needs to
replace an indicator bound to an acid site of the solid, the
basicity thereof should be stronger than the basicity of the
indicator. In a usual titration method, when an indicator is first
added to an inorganic powder/benzene dispersion, the indicator
exhibits the acid color due to the solid acidity, and it is
preferable to leave it for a sufficient time until a reaction is
completed. Subsequently, dropwise addition of n-butylamine is
started, and the concentration of acid sites is calculated from the
amount of n-butylamine when the color of the indicator returns to
its original basic color.
[0024] More specifically, 0.5 g samples of an inorganic powder are
placed in 20 mL sample vials, 10 mL of benzene is added to each
thereof, and the vial is lightly shaken. 20 stepped amounts of 0.1
N n-butylamine are added thereto, and stirring is carried out by an
agitator. 24 hours thereafter, 0.5 mL of a 0.1% methyl red
indicator solution is added thereto, and change in color of the
indicator is examined. The amount of n-butylamine added in the
system in which the largest amount of n-butylamine has been added
among those systems where no change in color of the indicator is
observed is defined as the mount of base that has reacted with the
acid sites, and is expressed as the concentration of acid sites
(mmol/g). Here, N is also called normality, and is a commonly used
unit for a person skilled in the art, being defined by
normality=molar concentration.times.acid value of one molecule.
[0025] An inorganic substance having a high concentration of acid
sites is a solid having many acid sites on the surface. Specific
examples of inorganic substances having a high concentration of
acid sites include, but are not limited to, amorphous magnesium
silicate, .alpha.-type zirconium phosphate, layered titanium
phosphate, activated alumina, and activated titania.
[0026] In order for the anti-allergen agent of the present
invention to be applied to processing with various materials and
configurations, the average particle size is preferably 0.01 to 50
.mu.m, and more preferably 0.02 to 20 .mu.m. A powder having an
average particle size of at least 0.01 .mu.m has the advantage of
ease of handling since it does not easily reaggregate. Furthermore,
when dispersed in a binder, etc. and post-processed with a fiber,
particles having an average particle size of no greater than 50
.mu.m are preferable since they have good dispersibility, do not
degrade the texture of a fiber, and do not easily cause thread
breakage when kneaded with a fiber. An average representative value
for the particle size may be measured by means of a laser
diffraction particle size distribution analyzer, etc., and a median
diameter analyzed on a volumetric basis may be used as a
representative value for the particle size.
[0027] There is no restriction on the color tone of the
anti-allergen agent in the present invention, but in order to apply
it to processing with various materials and configurations, white
or a pale color having high lightness is preferable. The lightness
is preferably at least 60 as an L value when measured using a
colorimeter.
[0028] Furthermore, the inorganic substance forming the
anti-allergen agent in the present invention preferably has an acid
strength pKa of no greater than 1.5. This is because high
anti-allergen properties are exhibited if the acid strength as a
solid acid is high in addition to there being a high concentration
of acid sites. The acid strength of the anti-allergen agent
referred to in the present invention is the ability of an acid site
of the anti-allergen agent surface to donate a proton to a base or
the ability thereof to accept an electron pair from a base.
Measurement of acid strength may be carried out by a method
employing an indicator. Selecting an appropriate indicator as a
base enables acid strength to be measured in terms of the ability
to convert the base form of the indicator into its conjugate acid
form.
[0029] Examples of indicators that can be used in measurement of
acid strength and (pKa values) include methyl red (+4.8),
4-phenylazo-1-naphthylamine (+4.0), dimethyl yellow (+3.3),
2-amino-5-azotoluene (+2.0), 4-phenylazo-diphenylamine (+1.5),
4-dimethylaminoazo-1-naphthalene (+1.2), crystal violet (+0.8),
p-nitrobenzeneazo-p'-nitro-diphenylamine (+0.43), dicinnamylacetone
(-3.0), benzalacetophenone (-5.6), and anthraquinone (-8.2). Use of
such various acid-base conversion indicators whose acid strength
(pKa) is known enables acid strength to be measured. The lower the
pKa of the indicator whose color is changed, the higher the acid
strength.
[0030] A method for measuring the acid strength of an inorganic
solid acid employing the above-mentioned indicators is as
follows.
[0031] 0.1 g of a solid acid is weighed in a test tube, and 2 mL of
benzene is added thereto and mixed by gently shaking. Two drops of
a 0.1% benzene solution of an indicator (for crystal violet, a 0.1%
ethanol solution instead of a benzene solution) are added thereto
and mixed by gently shaking, and change of color is examined. The
acid strength of the solid acid is equal to or less than the
highest acid strength (that is, the lowest pKa value) where change
in color of the indicator is confirmed and greater than the lowest
acid strength (that is, the highest pKa value) where change in
color of the indicator is not confirmed, and the pKa value of the
inorganic solid acid is expressed as (highest pKa value where
change in color is not confirmed) to (lowest pKa value where change
in color is confirmed). Furthermore, where there is no appropriate
indicator for showing a lower limit, it is generally expressed as
being equal to or less than (lowest pKa value where change in color
is confirmed), and when there is no appropriate indicator for
showing an upper limit, it is expressed as being greater than
(highest pKa value where change in color is not confirmed).
[0032] The anti-allergen effect of the inorganic substance in the
present invention is easily exhibited when it has a defined
moisture content. The water content in the inorganic substance is
preferably at least 0.5 wt %, more preferably at least 2 wt %, and
yet more preferably at least 10 wt %. An inorganic substance having
hygroscopicity can retain moisture in the inorganic substance even
when it is mixed with another material or the humidity of the
atmosphere changes, and it is excellent in terms of having in the
inorganic substance itself the moisture necessary to inactivate an
allergen.
[0033] The anti-allergen effect of the present invention is
evaluated by a sandwich ELISA method, which is widely known as a
method for detecting/quantifying an antigen, and can be expressed
as the percentage allergen inactivation (units: %) shown in
<Equation 1>. The initial amount of allergen means the amount
of allergen used in an ELISA evaluation and evaluated without using
a sample, and the amount of allergen remaining means the amount of
allergen after contacting a sample. Furthermore, the allergen
inactivation referred to in the present invention means suppression
of a reaction between the allergen and a specific antibody, and the
higher the percentage allergen inactivation, the more preferable it
is. Specifically, the percentage allergen inactivation is
preferably 90% or greater, and more preferably 99% or greater.
Percentage allergen inactivation=(1-amount of allergen
remaining/initial amount of allergen).times.100(%) <Equation
1>
[0034] The configuration of use of the anti-allergen agent of the
present invention is not particularly limited, and it may be mixed
with another component or compounded with another material as
appropriate according to the intended application. For example, it
may be used in various configurations such as powder,
powder-containing dispersion, powder-containing particles,
powder-containing paint, powder-containing fiber, powder-containing
paper, powder-containing plastic, powder-containing film, and
powder-containing aerosol and, furthermore, if necessary various
types of additives and materials such as a deodorant, an
antimicrobial agent, an antifungal agent, a flame retardant, a
corrosion inhibitor, a fertilizer, and a building material may be
used in combination. Furthermore, addition to a material for which
there is a possibility of it being in human contact, such as for
example resin, paper, plastic, rubber, glass, metal, concrete,
timber, paint, fiber, leather, or stone, makes it possible to
inactivate allergens in a living space.
[0035] Among these application methods, use of the anti-allergen
agent of the present invention as a coating composition containing
a fixing agent (binder) is preferable. This coating composition may
contain an additive in addition to the binder, and the coating
composition may be diluted with a solvent or water before
processing therewith a product with various types of shapes. On the
one hand the larger the anti-allergen agent/binder solids content
ratio by weight in the coating composition of the present
invention, the easier it is for an effect to be exhibited, but on
the other hand the larger the binder solids content ratio by
weight, the more strongly the anti-allergen agent is fixed and the
harder it is for the power to fall off. Therefore, the
anti-allergen agent/binder solids content ratio by weight in the
coating composition containing the anti-allergen agent is
preferably 90/10 to 30/70, and more preferably 80/20 to 50/50.
[0036] When the coating composition is used by dilution, from the
viewpoint of ease of dispersion and good storage stability, the
concentration of the anti-allergen agent contained in the
composition is preferably 0.5 to 50 mass %, and more preferably 1
to 30 mass %. Since an anti-allergen effect is usually exhibited by
contact between an anti-allergen agent and an allergen on the
surface of a product with various types of shape, fixing an
anti-allergen agent to the surface of a product by means of the
coating composition is preferable to it being used in the entire
interior of a product because a large effect can be obtained with a
smaller amount of anti-allergen agent.
[0037] The binder used in the coating composition of the present
invention includes those below. That is, there are a natural resin,
a natural resin derivative, a phenolic resin, a xylene resin, a
urea resin, a melamine resin, a ketone resin, a coumarone/indene
resin, a petroleum resin, a terpene resin, cyclized rubber,
chlorinated rubber, an alkyd resin, a polyamide resin, polyvinyl
chloride, an acrylic resin, a vinyl chloride/vinyl acetate
copolymer resin, polyvinyl acetate, polyvinyl alcohol, polyvinyl
butyral, chlorinated polypropylene, a styrene resin, an epoxy
resin, urethane and cellulose derivatives, etc. Among them, an
acrylic resin, polyvinyl chloride, and a vinyl chloride/vinyl
acetate copolymer resin are preferable, and an emulsion type resin
is particularly preferable since it is less polluting and easy to
handle.
[0038] Furthermore, examples of those that can be used as an
additive include a pigment such as zinc oxide or titanium oxide, a
dye, an antioxidant, a light stabilizer, a flame retardant, an
antistatic agent, a foaming agent, an impact modifier, glass fiber,
a lubricant such as a metallic soap, a desiccant, an extending
agent, a coupling agent, a nucleating agent, a flowability
improving agent, a deodorant, wood flour, a fungicide, an
antifoulant, a corrosion inhibitor, a metal powder, a UV absorber,
and a UV shielding agent.
[0039] As a method for processing a fiber using a coating
composition comprising the anti-allergen agent of the present
invention, there is a method in which a fiber or a fiber product is
coated with, immersed in, or sprayed with the coating composition
as it is or a diluted liquid thereof. There is no limitation to the
fiber that can be processed, and examples thereof include natural
fibers such as cotton, silk, and wool, synthetic fibers such as
polyester, nylon, and acrylonitrile, semi-synthetic fibers such as
triacetate and diacetate, and recycled fibers such as viscose
rayon, and a composite fiber employing two or more types of the
above fibers may be used. Moreover, use with a nonwoven fabric
employing polyethylene, polypropylene, etc. is also possible. A
method for processing a fiber or a fiber product with the
anti-allergen agent of the present invention is not particularly
limited; there are an immersion treatment, a printing treatment, a
spraying treatment, etc., and processing is completed by drying the
fiber containing the composition. A drying method may employ any
method such as natural drying, hot air drying, or vacuum drying,
and an anti-allergen agent may be fixed to a fiber preferably by a
drying method involving heating at 40.degree. C. to 250.degree. C.,
and preferably 50.degree. C. to 180.degree. C., for 1 min. to 5
hours, and preferably for 5 minutes to 3 hours.
[0040] When the amount of anti-allergen agent of the present
invention attached to a fiber or a fiber product is at least 0.1 g
per m.sup.2 of the fiber or fiber product, an effect can be
exhibited. On the other hand, in order to prevent the physical
properties and texture of the fiber or fiber product from being
degraded, it is preferably no greater than 20 g/m.sup.2, and is
more preferably 1 g to 10 g/m.sup.2.
[0041] When the pH of the coating composition comprising the
anti-allergen agent of the present invention is too low, metal of
production equipment might be corroded, a processing solution might
be degraded, or its stability might be impaired, whereas when the
pH is too high, the solid acid is neutralized and the anti-allergen
effect might be decreased; when the coating composition is an
aqueous system, etc. and measurement of pH is possible, the pH is
preferably at least 3 but no greater than 9. The main factors for
determining the pH of a coating composition are the same as those
for the pH of an aqueous dispersion of an inorganic powder and are
greatly influenced by the pKa of the solid acid, but they are also
influenced by the concentration of acid sites, the solubility or
hydrophilicity of the anti-allergen agent itself, or a component,
other than the anti-allergen agent, forming the coating
composition, and it is difficult to predict the pH; when the pH is
too low, the dispersion itself containing the coating composition
becomes acidic, if it becomes attached to a metal section of
processing equipment, rust might be formed, and the effect of a
dispersant might be degraded, thus causing the dispersion to form a
precipitate.
[0042] Furthermore, when the coating composition comprising the
anti-allergen agent of the present invention is a nonaqueous system
or is used as a paint comprising various types of paint component
or when it is used as a resin composition comprising the
anti-allergen agent, a metal section with which it is in contact
might be similarly corroded, or change in color of a resin might
occur; it has been found that, in a test as an aqueous dispersion
system, one that gives a pH in a fixed range is preferable since
hardly any rust or change in color occur. As such a test as an
aqueous dispersion system, a method in which an anti-allergen agent
is dispersed in water and its pH is measured is an easy method. For
example, an anti-allergen agent is dispersed in deionized water at
5 wt %, the pH after stirring at 25.degree. C. for 5 min. by means
of a stirrer may be measured using a glass electrode pH meter, and
the pH thus obtained is preferably at least 3 but no greater than
9. A coating composition, a paint, a resin, etc. employing such an
anti-allergen agent is preferable since hardly any metal corrosion
or change in color occurs. Since a paint is a composition for the
purpose of coating, it is one type of coating composition, but in
particular a coating composition that is not only for the purpose
of fixing a functional component such as an anti-allergen agent but
also for exhibiting weatherability or protection or for the
aesthetic appearance of an article surface while a coating itself
formed by curing the composition has a certain strength is called a
paint.
[0043] The anti-allergen agent of the present invention can be used
by adding it to a paint. The paint may contain various types of
additive. Examples of a resin component of the paint include oils
such as soybean oil, linseed oil, safflower oil, and castor oil,
natural resins such as rosin, copal, and shellac, processed resins
such as a chroman resin and a petroleum resin, synthetic resins
such as an alkyd resin, an acrylic resin, an epoxy resin, a
polyurethane resin, a vinyl chloride resin, a silicone resin, and a
fluorine resin, rubber derivatives such as a chlorinated rubber and
a cyclized rubber, and cellulose derivatives such as cellulose
nitrate (lacquer) and acetyl cellulose. Examples of a pigment of
the paint include colorant pigments such as (white) titanium,
(black) carbon, (brown) red iron oxide, (vermillion) chrome
vermillion, (blue) Prussian blue, (yellow) chrome yellow, and (red)
iron oxide, extender pigments such as calcium carbonate, talc, and
baryta powder, anticorrosive pigments such as red lead, lead
suboxide, and lead cyanamide, and functional pigments such as
aluminum powder and zinc sulfide (fluorescent pigment). Examples of
paint additives include a UV-curing agent, a plasticizer, a
dispersant, an antisettling agent, an emulsifying agent, a
thickener, an antifoaming agent, an anti-mold agent, a
preservative, an antiskinning agent, a desiccant, an antidrip
agent, a delustering agent, an antistatic agent, a conductive
agent, a flame retardant, and an antigraffiti agent. Examples of a
solvent of the paint include water, an alcohol, and a thinner such
as a paint thinner, a lacquer thinner, or a thinner for a
polyurethane resin, and a paint may be prepared by combining the
above.
[0044] As a method for processing a substrate with a paint
comprising the anti-allergen agent of the present invention, a
pre-produced substrate may be coated with a paint as it is or as a
liquid after dilution by means of a brush application technique, a
roller technique, a spraying technique, a trowel application
technique, etc. Furthermore, the applied paint may be cured by
exposure to UV. There are various types of substrate that can be
processed, examples thereof including various types of plastics
such as polyethylene, polyvinyl chloride, polyvinylidene chloride,
polyvinyl alcohol, polypropylene, polyester, polycarbonate,
polystyrene, polyacrylonitrile, and cellophane, a vinyl chloride
sheet, a jointing compound such as a modified silicone or urethane,
metal, ceramic siding, porcelain, stone, earthenware, glazed tiles,
marble, granite, and glass.
[0045] When the anti-allergen agent/paint solids content ratio by
weight in a paint comprising the anti-allergen agent of the present
invention is at least 10/90, a clear effect can easily be
exhibited. Furthermore, in terms of economic reasons or the
physical properties and texture of a substrate to be painted not
being degraded, or in terms of the physical properties and function
of the paint not being greatly impaired, it is preferably no
greater than 50/50. Therefore, the anti-allergen agent/paint solids
content ratio by weight in a paint comprising the anti-allergen
agent of the present invention is preferably 10/90 to 50/50, and
more preferably 20/80 to 40/60.
[0046] The anti-allergen resin composition may easily be obtained
by combining the anti-allergen agent of the present invention with
a resin. The type of resin that can be used is not particularly
limited; any of a natural resin, a synthetic resin, and a
semi-synthetic resin may be used and, moreover, either of a
thermoplastic resin or a thermosetting resin may be used.
Specifically, the resin may be any of a resin for molding, a resin
for fiber, and a rubber-form resin, and examples thereof include
resins for molding or fiber such as polyethylene, polypropylene,
vinyl chloride, an ABS resin, an AS resin, an MBS resin, a nylon
resin, polyester, polyvinylidene chloride, polystyrene, polyacetal,
polycarbonate, PBT, an acrylic resin, a fluorine resin, a
polyurethane elastomer, a polyester elastomer, melamine, a urea
resin, a tetrafluoroethylene resin, an unsaturated polyester resin,
rayon, acetate, acrylic, polyvinyl alcohol, cupra, triacetate, and
vinylidene, and rubber-form resins such as natural rubber, silicone
rubber, styrene butadiene rubber, ethylene propylene rubber,
fluorine rubber, nitrile rubber, chlorosulfonated polyethylene
rubber, butadiene rubber, synthetic natural rubber, butyl rubber,
urethane rubber, and acrylic rubber. Moreover, in addition to a
resin component, various types of additives may be added. Examples
of additives that can be used include a pigment such as zinc oxide
or titanium oxide, a dye, an antioxidant, a light stabilizer, a
flame retardant, an antistatic agent, a foaming agent, an impact
modifier, glass fiber, a lubricant such as a metallic soap, a
desiccant, an extending agent, a coupling agent, a nucleating
agent, a flowability improving agent, a deodorant, wood flour, a
fungicide, an antifoulant, a corrosion inhibitor, a metal powder, a
UV absorber, and a UV shielding agent, and any thereof may be used
preferably.
[0047] A method for producing a resin composition by combining the
anti-allergen agent of the present invention with a resin may
employ any known method. For example, there are (1) a method in
which an attachment agent for making it easy for an anti-allergen
agent powder to become attached to a resin or a dispersant for
improving the dispersibility of an anti-allergen agent powder is
used, and a pellet-form resin or a powder-form resin is directly
mixed by a mixer, (2) a method in which mixing is carried out as
described above, molding into pellets is carried out using an
extruder, and the resulting molding is then combined with a
pellet-form resin, (3) a method in which an anti-allergen agent is
molded into high concentration pellet form using a wax, and the
resulting pellet-form molding is then combined with a pellet-form
resin, (4) a method in which a paste-form composition is prepared
by dispersion-mixing an anti-allergen agent in a highly viscous
liquid such as a polyol, and this paste is then combined with a
pellet-form resin, etc.
[0048] Molding of the above-mentioned resin composition may employ
any known molding technique and mechanical equipment commensurate
with the properties of various types of resins, and preparation may
be carried out easily by a method involving mixing, incorporating,
or kneading while heating and applying pressure or vacuum at an
appropriate temperature or pressure; specific procedures therefor
may employ standard methods, and moldings can be obtained in
various forms such as clump form, sponge form, film form, sheet
form, thread form, pipe form, or a composite form thereof. When the
anti-allergen agent/resin composition solids content ratio by
weight in a resin composition containing the anti-allergen agent of
the present invention is at least 10/90, a clear effect can easily
be exhibited. Furthermore, in terms of economic reasons,
moldability of the resin composition, or physical properties and
texture of a molding not being degraded, it is preferably no
greater than 50/50. Therefore, the anti-allergen agent/resin
composition solids content ratio by weight in a resin composition
containing the anti-allergen agent of the present invention is
preferably 10/90 to 50/50, and more preferably 20/80 to 40/60.
[0049] With regard to the configuration of use of the anti-allergen
agent of the present invention, other than the above-mentioned
composition, resin composition, and resin molding, it may be used
as it is, as a mixture with another component as appropriate, or as
a composite with another material, according to the intended
application in which it is necessary to suppress an allergen. For
example, it may be used in any form such as powder form, powder
dispersion form, granular form, aerosol form, or liquid form.
[0050] The anti-allergen agent of the present invention may be
utilized in various fields where suppression of an allergen is
required, that is, interior goods, bedding, filters, furniture,
vehicle interior goods, fiber products, house building products,
paper products, toys, leather products, toiletry products,
cosmetics, and other products. Examples thereof include interior
goods such as carpets, curtains, wallpaper, tatami, screen paper,
floor wax, and calendars, bedding such as duvets, beds, sheets,
pillows, and pillow covers, filters for air cleaners or air
conditioners, furniture such as sofas and chairs, vehicle interior
goods such as child seats and passenger seats, dustbags for vacuum
cleaners, clothing, masks, soft toys, and kitchen goods, but the
examples are not limited thereto.
[0051] Compared with existing anti-allergen agents, the
anti-allergen agent of the present invention not only exhibits high
anti-allergen activity but also exhibits excellent heat resistance
due to it being an inorganic substance, has little coloration or
change in color, and is not leached out by water, and it therefore
has durability. It can impart excellent anti-allergen properties to
various products by simple processing methods.
EXAMPLES
[0052] The present invention is explained in further detail by
reference to Examples below, but the Examples should not be
construed as limiting the present invention.
[0053] The average particle size of an inorganic powder described
in the Examples means median diameter on a volumetric basis
obtained by ultrasonically dispersing in deionized water and
measuring by means of a laser diffraction particle size
distribution meter, % means mass % unless otherwise specified, and
the units of % for the percentage allergen inactivation are those
obtained from <Equation 1>.
[0054] With regard to measurement of the concentration of acid
sites, 0.5 g samples of an inorganic powder were placed in 20 mL
sample vials, 10 mL of benzene was added to each thereof, and the
vials were lightly shaken. 20 stepped amounts of 0.1 N n-butylamine
were added thereto, and stirring was carried out by an agitator. 24
hours thereafter, 0.5 mL of a 0.1% methyl red solution diluted with
benzene was added thereto, and change in color of the methyl red
was examined visually. The amount of n-butylamine added that was
the largest amount of n-butylamine added where no change in color
of methyl red was observed was defined as the amount of base that
had reacted with the acid sites, and was expressed as the
concentration of acid sites (mmol/g).
[0055] Measurement of acid strength was carried out by weighing 0.1
g of a sample in a test tube, adding 2 mL of benzene and two drops
of a 0.1% benzene solution of an indicator (0.1% ethanol solution
for crystal violet), lightly shaking so as to mix them, and
examining for change of color. Since the acid strength can be
considered to be equal to or less than the highest acid strength
for which change in color of the indicator is observed (lowest pKa
value) and greater than the lowest acid strength for which change
in color of the indicator is not observed (highest pKa), this range
was recorded as the pKa value. The indicators used were methyl red
(pKa=4.8), 4-phenylazo-1-naphthylamine (pKa=4), dimethyl yellow
(pKa=3.3), 4-phenylazo-diphenylamine (pKa=1.5), crystal violet
(pKa=0.8), dicinnamylacetone (pKa=-3), benzalacetophenone
(pKa=-5.6), and anthraquinone (pKa=-8.2).
[0056] With regard to the water content of an inorganic powder,
about 5 g of a sample was weighed (weighed to a precision of 0.1
mg) into an aluminum cup that had been taken to constant mass in a
dryer at 250.degree. C. for 1 hour, was dried in a dryer at
250.degree. C. for 2 hours, and was then weighed again (weighed to
a precision of 0.1 mg), the water content of the inorganic powder
being defined by the quotient, expressed as a %, obtained by
dividing the decrease due to drying by the mass before drying.
[0057] Anti-allergen effects were evaluated by a sandwich ELISA
method employing Dermatophagoides farinae allergen (allergen
generally called Derf2) and Cryptomeria japonica pollen allergen
(allergen generally called Cryj1). The test procedure when
Dermatophagoides farinae allergen was used was as follows.
Antibody-coated wells were prepared by a standard method using a
Dermatophagoides farinae allergen (Derf2)-specific antibody (15E11
antibody, Asahi Breweries, Ltd.). 3 mg of a sample was weighed, and
500 .mu.L of Dermatophagoides farinae allergen (Derf2) prepared at
40 ng/mL using an antigen diluent was added thereto. The mixture
was stirred well so as to contact the sample with the allergen and
was then subjected to centrifugation, and the supernatant was
collected, added to 15E11 antibody-coated wells that had been
treated with a blocking agent, and allowed to stand at room
temperature. After 1 hour, the sample was discarded, each well was
washed with washing buffer, 200 ng/mL of horseradish
peroxidase-labeled anti-Derf2 monoclonal antibody 13A4PO (Asahi
Breweries, Ltd.) that had been diluted with washing buffer was
added to each well, and the wells were allowed to stand at room
temperature. After 1 hour, the antibody liquid was discarded, each
well was washed with washing buffer, a substrate liquid was added
to each well, and the wells were allowed to stand at room
temperature. After 5 minutes, 2N sulfuric acid was added so as to
stop the reaction, and the absorbance at 490 nm was measured. The
results were expressed as percentage allergen inactivation of
various samples by determining the relationship between amount of
allergen and absorbance from an evaluation carried out without
using a sample, determining the amount of allergen remaining from
the absorbance obtained when evaluating various types of samples,
and calculating from <Equation 1> above.
[0058] The test procedure for the sandwich ELISA method when
Cryptomeria japonica pollen allergen was used was as follows.
Antibody-coated wells were prepared by a standard method using a
Cryptomeria japonica pollen allergen (Cryj1)-specific antibody
(Anti-Cryj1mAb013, Seikagaku Corporation). 3 mg of a sample was
weighed, and 500 .mu.L of Cryptomeria japonica pollen allergen
(Cryj1) prepared at 10 ng/mL using an antigen diluent was added
thereto. The mixture was stirred well so as to contact the sample
with the allergen and was then subjected to centrifugation, and the
supernatant was collected, added to Anti-Cryj1mAb013
antibody-coated wells that had been treated with a blocking agent,
and allowed to stand at room temperature. After 1 hour, the sample
was discarded, each well was washed with washing buffer, 250 ng/mL
of horseradish peroxidase-labeled anti-Cryj1 monoclonal antibody
053 (Seikagaku Corporation) that had been diluted with washing
buffer was added to each well, and the wells were allowed to stand
at room temperature. After 2 hours, the antibody liquid was
discarded, each well was washed with washing buffer, a substrate
liquid was added to each well, and the wells were allowed to stand
at room temperature. After 5 minutes, 2N sulfuric acid was added so
as to stop the reaction, and the absorbance at 490 nm was measured.
The results were expressed as percentage allergen inactivation of
various types of samples by calculating from Equation 1 by the same
method as for Dermatophagoides farinae allergen.
[0059] With regard to the pH of an aqueous dispersion of an
inorganic powder, the inorganic powder was dispersed in
ion-exchanged water in a beaker at 5 wt %, and the pH after
stirring at 25.degree. C. for 5 min. by means of a stirrer was
measured using a glass electrode pH meter.
[0060] With regard to a test for confirming change in color of a
resin molding, an inorganic powder was added at 2 wt % to a
polypropylene powder, and a plate was molded at 220.degree. C.
using an injection molding machine. The degree of coloration of the
plate thus obtained was examined visually.
[0061] With regard to a metal corrosivity test, a test piece made
of iron (width/length/thickness=20/80/2 mm) was first prepared and
the surface was washed with acetone. The test piece made of iron
and a 5 wt % aqueous dispersion of an inorganic powder were placed
in a glass test tube having a diameter of 30 mm, and it was set in
a heating block adjusted to 60.degree. C. 24 hours thereafter, the
test piece was taken out, immersed in distilled water,
ultrasonically washed for 5 min., then dried in a dryer at
50.degree. C. for 30 min., and presence or absence of rust on the
test piece was examined visually.
[0062] The anti-allergen effect of a processed fiber product was
evaluated as percentage anti-allergen inactivation from Equation 1
above by using Cryptomeria japonica pollen allergen (Cryj1) as the
allergen, placing 25 cm.sup.2 of the fiber in a reclosable plastic
bag, contacting the sample with 1 mL of a 100 ng/mL allergen
solution for 1 hour, then centrifuging the contacted liquid,
collecting a supernatant, measuring the absorbance by evaluation
involving the same ELISA method as for an inorganic powder, and
comparing with the absorbance when no sample was used.
[0063] The anti-allergen effect of a resin-kneaded film was
evaluated as percentage anti-allergen inactivation from Equation 1
above by using Cryptomeria japonica pollen allergen (Cryj1) as the
allergen, placing 25 cm.sup.2 of the film in a reclosable plastic
bag, contacting the sample with 1 mL of a 10 ng/mL allergen
solution for 1 hour, then centrifuging the contacted liquid,
collecting a supernatant, measuring the absorbance by evaluation
involving the same ELISA method as for an inorganic powder, and
comparing with the absorbance when no sample was used.
[0064] The anti-allergen effect of a film processed with an acrylic
UV-curing paint was evaluated as percentage anti-allergen
inactivation from Equation 1 above by using Cryptomeria japonica
pollen allergen (Cryj1) as the allergen, placing 25 cm.sup.2 of the
film in a reclosable plastic bag, contacting the sample with 1 mL
of a 10 ng/mL allergen solution for 3 hours, then centrifuging the
contacted liquid, collecting a supernatant, measuring the
absorbance by evaluation involving the same ELISA method as for an
inorganic powder, and comparing with the absorbance when no sample
was used.
Example 1
Amorphous Magnesium Silicate
[0065] An amorphous magnesium silicate (SiO.sub.2/MgO=1.3) was
obtained by filtering a precipitate obtained using as starting
materials magnesium sulfate and water glass, washing it with water,
drying, and grinding. The amorphous magnesium silicate thus
obtained was subjected to measurement of average particle size,
water content, acid strength, and mite allergen inactivating effect
and Cryptomeria japonica pollen allergen inactivating effect by the
ELISA method, and the results are shown in Table 1. Furthermore,
the results of measurement of color tone, pH of a 5 wt % aqueous
dispersion, coloration of a PP plate, and metal corrosivity are
shown in Table 2.
Example 2
.alpha.-Type Zirconium Phosphate
[0066] An .alpha.-type zirconium phosphate powder was obtained by
adding a 15% zirconium oxychloride aqueous solution to a 75%
phosphoric acid aqueous solution, carrying out aging at 120.degree.
C. for 12 hours, then filtering a precipitate, washing it with
water, drying, and grinding. The .alpha.-type zirconium phosphate
thus obtained was subjected to measurement of average particle
size, water content, acid strength, and mite allergen inactivating
effect and Cryptomeria japonica pollen allergen inactivating effect
by the ELISA method, and the results are shown in Table 1.
Furthermore, the results of measurement of color tone, pH of a 5 wt
% aqueous dispersion, coloration of a PP plate, and metal
corrosivity are shown in Table 2.
Example 3
Activated Titanium Oxide
[0067] An activated titanium oxide was prepared by filtering a
precipitate obtained using as starting materials titanyl sulfate
and oxalic acid, drying, calcining at 500.degree. C., and then
grinding. The titanium oxide thus obtained was subjected to
measurement of average particle size, water content, acid strength,
and mite allergen inactivating effect and Cryptomeria japonica
pollen allergen inactivating effect by the ELISA method, and the
results are shown in Table 1. Furthermore, the results of
measurement of color tone, pH of a 5 wt % aqueous dispersion,
coloration of a PP plate, and metal corrosivity are shown in Table
2.
Example 4
Activated Kaolin
[0068] A commercial activated kaolin (Galleon Earth SH, Mizusawa
Industrial Chemicals, Ltd.) was subjected to measurement of average
particle size, acid strength, and mite allergen inactivating effect
and Cryptomeria japonica pollen allergen inactivating effect by the
ELISA method, and the results are shown in Table 1. Furthermore,
the results of measurement of color tone, pH of a 5 wt % aqueous
dispersion, coloration of a PP plate, and metal corrosivity are
shown in Table 2.
Comparative Example 1
Amorphous Magnesium Silicate
[0069] An amorphous magnesium silicate (SiO.sub.2/MgO=3.9) was
obtained by filtering a precipitate obtained using as starting
materials magnesium sulfate and water glass, washing it with water,
drying, and grinding. The crystalline magnesium silicate thus
obtained was subjected to measurement of average particle size,
water content, acid strength, and mite allergen inactivating effect
and Cryptomeria japonica pollen allergen inactivating effect by the
ELISA method, and the results are shown in Table 1. Furthermore,
the results of measurement of color tone, pH of a 5 wt % aqueous
dispersion, coloration of a PP plate, and metal corrosivity are
shown in Table 2.
Comparative Example 2
.gamma.-Type Zirconium Phosphate
[0070] A .gamma.-type zirconium phosphate was obtained by adding a
zirconium carbonate aqueous solution to a 75% phosphoric acid
aqueous solution, carrying out refluxing by heating at 98.degree.
C. for 24 hours, then filtering a precipitate, washing it with
water, drying, and grinding. The .gamma.-type zirconium phosphate
thus obtained was subjected to measurement of average particle
size, water content, acid strength, and mite allergen inactivating
effect and Cryptomeria japonica pollen allergen inactivating effect
by the ELISA method, and the results are shown in Table 1.
Furthermore, the results of measurement of color tone, pH of a 5 wt
% aqueous dispersion, coloration of a PP plate, and metal
corrosivity are shown in Table 2.
Comparative Example 3
NASICON-Type Zirconium Phosphate
[0071] A NASICON-type zirconium phosphate was obtained by adding
oxalic acid and a 75% phosphoric acid aqueous solution to a
zirconium oxychloride aqueous solution, adjusting the pH to 2.7
using sodium hydroxide, then carrying out refluxing by heating at
98.degree. C. for 12 hours, then filtering a precipitate, washing
it with water, drying, and grinding. The NASICON-type zirconium
phosphate thus obtained was subjected to measurement of average
particle size, water content, acid strength, and mite allergen
inactivating effect and Cryptomeria japonica pollen allergen
inactivating effect by the ELISA method, and the results are shown
in Table 1. Furthermore, the results of measurement of color tone,
pH of a 5 wt % aqueous dispersion, coloration of a PP plate, and
metal corrosivity are shown in Table 2.
Comparative Example 4
Titanium Oxide
[0072] A commercial titanium oxide (MC-50, Ishihara Sangyo Kaisha
Ltd.) was subjected to measurement of average particle size, acid
strength, and mite allergen inactivating effect and Cryptomeria
japonica pollen allergen inactivating effect by the ELISA method,
and the results are shown in Table 1. Furthermore, the results of
measurement of color tone, pH of a 5 wt % aqueous dispersion,
coloration of a PP plate, and metal corrosivity are shown in Table
2.
Comparative Example 5
Activated Alumina
[0073] A commercial activated alumina (GNDY-2, Mizusawa Industrial
Chemicals, Ltd.) was subjected to measurement of average particle
size, acid strength, and mite allergen inactivating effect and
Cryptomeria japonica pollen allergen inactivating effect by the
ELISA method, and the results are shown in Table 1. Furthermore,
the results of measurement of color tone, pH of a 5 wt % aqueous
dispersion, coloration of a PP plate, and metal corrosivity are
shown in Table 2.
Comparative Example 6
Silica-Alumina
[0074] A silica-alumina was prepared by stirring water glass and
aluminum nitrate as starting materials at 98.degree. C., calcining
a precipitate obtained at 400.degree. C., and then grinding. The
silica-alumina thus obtained was subjected to measurement of
average particle size, water content, acid strength, and mite
allergen inactivating effect and Cryptomeria japonica pollen
allergen inactivating effect by the ELISA method, and the results
are shown in Table 1. Furthermore, the results of measurement of
color tone, pH of a 5 wt % aqueous dispersion, coloration of a PP
plate, and metal corrosivity are shown in Table 2.
Comparative Example 7
Aluminum Phosphate
[0075] A commercial aluminum phosphate (K-WHITE 105, Tayca
Corporation) was subjected to measurement of average particle size,
acid strength, and mite allergen inactivating effect and
Cryptomeria japonica pollen allergen inactivating effect by the
ELISA method, and the results are shown in Table 1. Furthermore,
the results of measurement of color tone, pH of a 5 wt % aqueous
dispersion, coloration of a PP plate, and metal corrosivity are
shown in Table 2.
Comparative Example 8
Hydrotalcite
[0076] A commercial hydrotalcite (HT-P, Sakai Chemical Industry
Co., Ltd.) was subjected to measurement of average particle size,
acid strength, and mite allergen inactivating effect and
Cryptomeria japonica pollen allergen inactivating effect by the
ELISA method, and the results are shown in Table 1. Furthermore,
the results of measurement of color tone, pH of a 5 wt % aqueous
dispersion, coloration of a PP plate, and metal corrosivity are
shown in Table 2.
TABLE-US-00001 TABLE 1 Average Acid site Percentage allergen
particle Water concentration inactivation (%) Inorganic powder size
(.mu.m) content % (mmol/g) pKa Derf2 Cryj1 Ex. 1 Amorphous 5.5 10
0.07 0.8 to 1.5 >99 >99 magnesium silicate Ex. 2 .alpha.-Type
zirconium 0.2 5 0.01 -8.2 to -5.6 99 99 phosphate Ex. 3 Activated
titanium 0.01 6.5 0.02 4.0 to 3.3 99 99 oxide Ex. 4 Activated
kaolin 5.2 7 0.002 <-8.2 99 99 Comp. Ex. 1 Amorphous 2.8 6.8
<0.001 0.8 to 1.5 <10 <10 magnesium silicate Comp. Ex. 2
.gamma.-Type zirconium 1 3.1 <0.001 -8.2 to -5.6 45 40 phosphate
Comp. Ex. 3 NASICON-type 1 0.4 <0.001 -8.2 to -5.6 35 20
zirconium phosphate Comp. Ex. 4 Commercial 0.02 0.4 <0.001 -5.6
to -3.0 85 65 titanium oxide Comp. Ex. 5 Activated alumina 0.4 1.8
<0.001 0.8 to 1.5 <10 <10 Comp. Ex. 6 Silica-alumina 5.4 9
<0.001 0.8 to 1.5 30 25 Comp. Ex. 7 Aluminum 0.3 6.9 <0.001
4.0 to 3.3 <10 <10 phosphate Comp. Ex. 8 Hydrotalcite 4.4 4.8
<0.001 >4.8 <10 <10
TABLE-US-00002 TABLE 2 Color Coloration when Metal Component tone
pH kneading resin corrosivity Ex. 1 Amorphous magnesium White 8
None None silicate Ex. 2 .alpha.-Type zirconium White 3 None None
phosphate Ex. 3 Activated titanium oxide White 6 None None Ex. 4
Activated kaolin White 2 Black discoloration Rusted Comp. Ex. 1
Amorphous magnesium White 8 None None silicate Comp. Ex. 2
.gamma.-Type zirconium White 3 None None phosphate Comp. Ex. 3
NASICON-type zirconium White 4 None None phosphate Comp. Ex. 4
Commercial titanium White 2 Brown discoloration Rusted oxide Comp.
Ex. 5 Activated alumina White 5 None None Comp. Ex. 6
Silica-alumina White 6 None None Comp. Ex. 7 Aluminum phosphate
White 6 None None Comp. Ex. 8 Hydrotalcite White 9 Yellow
discoloration None
[0077] From the results in Table 1, all of the inorganic powders
having a concentration of acid sites of 0.001 mmol/g or higher of
the present invention showed a percentage mite allergen
inactivation of 99% or greater. In particular, the amorphous
magnesium silicate having a concentration of acid sites of 0.07
mmol/g exhibited the effect of the percentage allergen inactivation
being greater than 99%, and was truly excellent as an anti-allergen
agent.
[0078] Furthermore, in the case of Cryptomeria japonica pollen
allergen, as in the case of mite allergen, the anti-allergen agent
of the present invention exhibited a high percentage allergen
inactivation and was truly excellent as an anti-allergen agent. On
the other hand, in the Comparative Examples, where the
concentration of acid sites was equal to or less than 0.001, hardly
any anti-allergen activity was exhibited.
[0079] Moreover, from the results of Table 2, the dispersions of
Example 4 and Comparative Example 4 had a pH for a 5 wt %
dispersion of less than 3 and exhibited metal corrosivity.
Example 7
Evaluation of Anti-Allergen Activity of Fiber-Fixed Example 1
[0080] The amorphous magnesium silicate that was the inorganic
substance of Example 1 and an acrylic emulsion binder (NW-7060,
Toagosei Co., Ltd., solids content 50%,) were mixed at a solids
content ratio by mass of 2:1 and applied to a fabric (components:
cotton/acrylic fiber=1/1) by immersion for 5 min. and then dried at
120.degree. C. for 30 min., thus preparing an anti-allergen fabric
having an amount of amorphous magnesium silicate fixed of 1
g/m.sup.2. The Cryptomeria japonica pollen allergen inactivating
effect of the anti-allergen fabric was measured, and the result is
shown in Table 3.
Example 8
Evaluation of Anti-Allergen Activity of Fiber-Fixed Example 1
[0081] The amorphous magnesium silicate that was the inorganic
substance of Example 1 and (NW-7060, Toagosei Co., Ltd., solids
content 50%,) were mixed at a solids content ratio by mass of 2:1
and applied to a fabric (components: cotton/acrylic fiber=1/1) by
immersion for 5 min. and then dried at 120.degree. C. for 30 min.,
thus preparing an anti-allergen fabric having an amount fixed of 2
g/m.sup.2. The Cryptomeria japonica pollen allergen inactivating
effect of the anti-allergen fabric was measured, and the result is
shown in Table 3.
Comparative Example 9
Evaluation of Anti-Allergen Activity when Example 1 was not Fixed
to Fiber
[0082] A comparative fabric was prepared by the same processing
method as in Example 7 without using the amorphous magnesium
silicate that was the inorganic substance of Example 1. The
Cryptomeria japonica pollen allergen inactivating effect of the
comparative fabric was measured, and the result is shown in Table
3
TABLE-US-00003 TABLE 3 Inorganic substance and Percentage allergen
amount fixed inactivation (%) Ex. 7 Magnesium silicate 1 g/m.sup.2
97 Ex. 8 Magnesium silicate 2 g/m.sup.2 >99 Comp. Ex. 9 Binder
only 15
[0083] From the results in Table 3, it was found that the
anti-allergen processed fabrics to which the amorphous magnesium
silicate of Example 1 was attached exhibited a percentage allergen
inactivation of greater than 99%. Therefore, the performance of the
anti-allergen products formed by post-processing a fiber with the
inorganic substance of the present invention was excellent.
Example 9
Evaluation of Heat Resistance of Fiber-Fixed Example 1
[0084] An anti-allergen fabric was prepared by the same method as
in Example 7 and subjected to heating at 120.degree. C. for 100
hours, and the Cryptomeria japonica pollen allergen inactivating
effect and color change of the anti-allergen fabric were then
measured, the results thereof being shown in Table 4.
Example 10
Evaluation of Heat Resistance of Fiber-Fixed Example 1
[0085] An anti-allergen fabric was prepared by the same method as
in Example 8 and subjected to heating at 120.degree. C. for 100
hours, and the Cryptomeria japonica pollen allergen inactivating
effect and color change of the anti-allergen fabric were then
measured, the results thereof being shown in Table 4.
TABLE-US-00004 TABLE 4 Percentage allergen inactivation (%) Change
in color Ex. 9 96 No change in color Ex. 10 >99 No change in
color
[0086] From the results of Table 4, since the anti-allergen
processed fabric to which the amorphous magnesium silicate of
Example 1 was attached exhibited a sufficiently high percentage
allergen inactivation even when heat was applied for a long time
and in addition exhibited hardly any change in color, the
anti-allergen product formed by post-processing a fiber with the
inorganic substance of the present invention had excellent heat
resistance.
Example 11
Evaluation of Water Resistance of Fiber-Fixed Example 1
[0087] An anti-allergen fabric was prepared by the same method as
in Example 7 and placed in a plastic container, ion-exchanged water
was added thereto, the container was shaken at 25.degree. C. for 16
hours, the anti-allergen fabric was dried at 120.degree. C. for 30
min., and the Cryptomeria japonica pollen allergen inactivating
effect thereof was measured, the results being shown in Table
5.
Example 12
Evaluation of Water Resistance of Fiber-Fixed Example 1
[0088] An anti-allergen fabric was prepared by the same method as
in Example 8 and placed in a plastic container, ion-exchanged water
was added thereto, the container was shaken at 25.degree. C. for 16
hours, the anti-allergen fabric was dried at 120.degree. C. for 30
min., and the Cryptomeria japonica pollen allergen inactivating
effect thereof was measured, the results being shown in Table
5.
TABLE-US-00005 TABLE 5 Percentage allergen inactivation (%) Ex. 11
97 Ex. 12 >99
[0089] From the results of Table 5, the anti-allergen processed
fabric to which the amorphous magnesium silicate of Example 1 was
attached exhibited a sufficiently high percentage allergen
inactivation even after being treated with water. Therefore, the
anti-allergen product formed by post-processing a fiber with the
inorganic substance of the present invention had excellent water
resistance as well.
Example 13
Evaluation of Anti-Allergen Activity of Resin-Kneaded Example 1
[0090] The amorphous magnesium silicate that was the inorganic
substance of Example 1 and powdered polypropylene were mixed at a
solids content ratio by mass of 10:90 and thermally pressed at
220.degree. C., thus preparing an anti-allergen film having a film
thickness of 0.2 mm. The results of measuring the Cryptomeria
japonica pollen allergen inactivating effect of the anti-allergen
film are shown in Table 6.
Example 14
Evaluation of Anti-Allergen Activity of Resin-Kneaded Example 1
[0091] The amorphous magnesium silicate that was the inorganic
substance of Example 1 and powdered polypropylene were mixed at
solids content ratio by mass of 20:80 and thermally pressed at
220.degree. C., thus preparing an anti-allergen film having a film
thickness of 0.2 mm. The results of measuring the Cryptomeria
japonica pollen allergen inactivating effect of the anti-allergen
film are shown in Table 6.
Comparative Example 10
Evaluation of Anti-Allergen Activity when Resin was not Kneaded
with Example 1
[0092] A comparative film was prepared by the same processing
method as in Example 13 without using the amorphous magnesium
silicate that was the inorganic substance of Example 1. The results
of measuring the Cryptomeria japonica pollen allergen inactivating
effect of the comparative film are shown in Table 6.
TABLE-US-00006 TABLE 6 Inorganic substance and Percentage allergen
amount added inactivation (%) Ex. 13 Magnesium silicate 10 wt % 50
Ex. 14 Magnesium silicate 20 wt % >99 Comp. Ex. Film only 0
10
[0093] From the results of Table 6, the anti-allergen processed
film that had been kneaded with the amorphous magnesium silicate of
Example 1 exhibited a high percentage allergen inactivation by the
addition of 20 wt % thereof. Therefore, the anti-allergen product
formed by kneading a resin with the inorganic substance of the
present invention had excellent performance.
Example 15
Evaluation of Anti-Allergen Activity of UV-Curing Resin-Processed
Example 1
[0094] The amorphous magnesium silicate that was the inorganic
substance of Example 1 and an acrylic UV-curing paint (without
solvent) were mixed at a solids content ratio by mass of 15:85, the
mixture was applied to a PET film (Lumirror T60-50, Toray) at a
thickness of 15 .mu.m using a bar coater, and irradiated with UV
using a high-pressure mercury lamp (intensity 60 W/cm) from a
distance of 25 cm at a conveyor speed of 3.7 m/min to thus cure the
composition, thereby preparing an anti-allergen film. The result of
measuring the Cryptomeria japonica pollen allergen inactivating
effect of the anti-allergen film is shown in Table 7.
Example 16
Evaluation of Anti-Allergen Activity of UV-Curing Resin-Processed
Example 1
[0095] The amorphous magnesium silicate that was the inorganic
substance of Example 1 and an acrylic UV-curing paint were mixed at
a solids content ratio by mass of 30:70, the mixture was applied to
a PET film (Lumirror T60-50, Toray) at a thickness of 15 .mu.m
using a bar coater, and irradiated with UV using a high-pressure
mercury lamp (intensity 60 W/cm) from a distance of 25 cm at a
conveyor speed of 3.7 m/min to thus cure the composition, thereby
preparing an anti-allergen film. The result of measuring the
Cryptomeria japonica pollen allergen inactivating effect of the
anti-allergen film is shown in Table 7.
Comparative Example 11
Evaluation of Anti-Allergen Activity of Film Processed with Acrylic
UV-Curing Paint when Example 1 was not Fixed Thereto
[0096] A comparative film was prepared by the same processing
method as in Example 15 without using the amorphous magnesium
silicate that was the inorganic substance of Example 1. The result
of measuring the Cryptomeria japonica pollen allergen inactivating
effect of the comparative film is shown in Table 7.
TABLE-US-00007 TABLE 7 Inorganic substance and Percentage allergen
amount added inactivation (%) Ex. 15 Magnesium silicate 15 wt % 50
Ex. 16 Magnesium silicate 30 wt % 80 Comp. Ex. Resin coating only
20 11
[0097] From the results of Table 7, the anti-allergen film that had
been coated with the amorphous magnesium silicate of Example 1 by
UV curing exhibited a high percentage anti-allergen inactivation.
Therefore, the anti-allergen product whose surface was processed by
UV curing with the inorganic substance of the present invention had
excellent performance.
Example 17
[0098] In order to carry out an evaluation of anti-allergen
properties in an actual application environment, the amorphous
magnesium silicate that was the inorganic substance and an acrylic
emulsion binder (NW-7060, Toagosei Co., Ltd., solids content 50 wt
%) were mixed at a solids content ratio by mass of 2:1 by the
method in accordance with Example 8, and a bath towel (155
cm.times.70 cm, component: cotton) was immersed therein for 5 min.
and then dried at 120.degree. C. for 60 min., thus preparing an
anti-allergen fabric (bath towel) having an amount fixed of 2
g/m.sup.2.
[0099] On a fine day on which Cryptomeria japonica pollen was
released, the bath towel was dried under the sun for 6 hours on an
outdoor dryer, thus adsorbing thereon Cryptomeria japonica pollen
floating in the environment. After allowing to stand overnight, the
entire surface of the bath towel was vacuumed using a vacuum
cleaner having a nonwoven fabric set therein, thus collecting the
allergen by vacuum on the nonwoven fabric. The allergen on the
nonwoven fabric was extracted with 10 mL of an antigen dilution
liquid (0.1% BSA+PBS buffer), and the amount of Cryptomeria
japonica pollen allergen (Cryj1) collected was measured by the
ELISA method, thus giving an amount of allergen collected. Since
the amount of natural Cryptomeria japonica pollen released changes
greatly according to the weather or the day, on other fine days
spaced by at least three days, the same adsorption test was carried
out three times, and the results of measuring the amount of
allergen collected are shown in Table 8. 1st, 2nd, and 3rd day in
Table 8 mean that the adsorption test was carried out on three
different days.
Comparative Example 12
[0100] A bath towel of Comparative Example 12 was prepared in the
same manner as in Example 17 except that only a binder that did not
contain the amorphous magnesium silicate was used, and Cryptomeria
japonica pollen floating in the environment was similarly adsorbed
thereon at the same place on the same days as for Example 17. The
results of measuring the amount of allergen collected are shown in
Table 8.
TABLE-US-00008 TABLE 8 Amount of allergen recovered (ng) 1st day
2nd day 3rd day Ex. 17 Magnesium silicate present 200 <10 65
Comp. Ex. 12 Binder only 795 130 145
[0101] Since for comparisons on the same day, the amount of
Cryptomeria japonica pollen attached to the bath towel of Example
17 can be considered to be at the same level as that of the bath
towel of Comparative Example 12, the result for the amount of
Cryptomeria japonica pollen allergen collected from the bath towel
of Example 17, to which the amorphous magnesium silicate was fixed,
being very low compared with the bath towel of Comparative Example
12, which did not have the amorphous magnesium silicate, suggests
that the attached Cryptomeria japonica pollen allergen was
inactivated by the amorphous magnesium silicate on the bath towel
of Example 17.
INDUSTRIAL APPLICABILITY
[0102] In accordance with use of the anti-allergen agent of the
present invention, it becomes possible to impart a function of
inactivating allergens derived from pollen, mites, etc. to a
material related to a human living space such as a fiber product or
a housing material, and an anti-allergen product can be
produced.
* * * * *